Agent for simultaneously dying and bringhtening keratin fibers

ABSTRACT

The present patent application concerns an agent for the simultaneous brightening and coloring of keratin fibers, said agent being characterized in that it contains at least one peroxy salt and at least one dye resistant to peroxy salts which is taken from the group consisting of azo dyes, quinone dyes, triphenylmethane dyes, nitro dyes, acid dyes and basic dyes.

The object of the present patent application is an agent forsimultaneous coloring and brightening of keratin fibers, for examplewool, silk or hair and particularly human hair.

Brightening and coloring formulations with direct and oxidative dyes areknown. As a result of the ammonia they contain and of the addition of aperoxide, these formulations bring about a brightening of 1 to 2 shadegradations. On previously dyed hair in particular, however, thebrightening with these formulations is only very slight. This lowbrightening efficacy greatly limits the number of achievable shades.

The objective was therefore to provide a brightening coloring agent thatwould permit a brightening of up to six shade gradations and a broadspectrum of shades. In particular, the brightening and coloring agentwas to be applicable to both natural hair and previously dyed hair.

We have now found that the aforesaid objective can be reached inoutstanding manner by use of a combination of certain direct dyes withperoxy salts that afford colorations with unusually good colorintensity, covering power and durability.

The object of the present invention therefore is an agent for thesimultaneous brightening and coloring of keratin fibers, said agentcontaining peroxy salts and peroxy salts-resistant dyes selected fromthe group consisting of azo dyes, quinone dyes, triphenylmethane dyes,acid dyes, basic dyes and nitro dyes.

The total amount of the afore-said direct dyes in the brighteningcolorant is from about 0.001 to 10 weight percent and particularly from0.002 to 8 weight percent. The concentration of these direct dyes in theready-to-use brightening agent that has been mixed with hydrogenperoxide is from about 0.0005 to 5 weight percent.

Useful direct dyes for the attainment of the desired color shades arecommon, physiologically harmless dyes resistant to peroxy salts andselected from the group consisting of azo dyes, quinone dyes,triphenylmethane dyes, acid dyes, basic dyes and nitro dyes or acombination thereof, for example:3-(2′,6′-diaminopyridyl-3′-azo)pyridine{=2,6-diamino-3-[(pyridin-3-yl)azo]pyridine};2-[(4-ethyl-(2-hydroxyethyl)amino]-2-methylphenyl)-azo]-5-nitro-1,3-thiazole(Disperse Blue 106);N,N-di(2-hydroxyethyl)-3-methyl4-[(4-nitro-phenyl)azo]aniline (DisperseRed 17, CI 11210);3-diethylamino-7-(4-dimethylamino-phenylazo)-5-phenylphenaziniumchloride (CI 11050); 4-(2-thiazolylazo)resorcinol; sodium4-[(4-phenylamino)azo]benzenesulfonate (Orange IV); 1-[(3-aminopropyl)amino-9,10-an-thracenedione (HC Red No. 8);3′,3″,4,5,5′,5″,6,7-octabromophenolsulfonephthalein (TetrabromophenolBlue);1-[(4-amino-3,5-dimethylphenyl)-(2,6-dichlorophenyl)methylene]-3,5-dimethyl-4-imino-2,5-cyclohexadienephosphoric acid (1:1) (Basic Blue 77);3′,3″,5′,5″-tetrabromo-m-cresolsulfonephthalein; disodium2,4-dinitro-1-naphthol-7-sulfonate (Acid Yellow 1; CI 10 316); sodium4-[(2′-hydroxy-1′-naphthyl)azo]benzenesulfonate (Acid Orange 7; CI 15510);3′,6′-dihydroxy-2′,4′,5′,7′-tetraiodospiro[isobenzofuran-1(3H),9′(9H)-xanthene]-3-onedisodium salt (Acid Red 51; CI 45 430); disodium6-hydroxy-5-[(2-methoxy-5-methyl-4-sulfophenyl)azo]-2-naphthalenesulfonate(FD&C Red 40; CI 16035); 2,4-dinitro-1-naphthol sodium salt (Acid Yellow24; CI 10315);2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachloro-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),9′(9H)xanthene]-3-onedisodium salt (Acid Red 92; CI 45410); sodium4-(2-hydroxy-1-naphthylazo)-3-methyl-benzenesulfonate (Acid Orange 8; CI15575); 2-amino-1,4-naphtalenedione; dithizone(1,5-diphenyl-thiocarbazone);N-(2-hydroxyethyl)-2-nitro-4-(trifluoromethyl)aniline (HC Yellow 13);N-(2-hydroxyethyl)-4-nitroaniline and4-chloro-N-(2,3-dihydroxypropyl)-2-nitroaniline.

The amount of dyes, based on the total amount of the brighteningcolorant, is from about 0.001 to 10 weight percent and particularly from0.002 to 8 weight percent.

Preferably used peroxy salts are the persulfates, for example, sodiumpersulfate, potassium per-sulfate, ammonium persulfate or mixtures ofthese persulfates.

The concentration of the peroxy salts in the brightening colorant isfrom about 0.1 to 50 weight percent and particularly from 1 to 40 weightpercent.

Other constituents of the brightening colorant of the invention are, ingeneral, surfactants and emulsifiers from the group of anionic, nonionicor ampholytic surface-active compounds, for example fatty alcoholsulfates, alkane sulfonates, olefin sulfonates, fatty alcohol polyglycolether sulfates, alkyl polyglycosides and ethoxylated fatty alcohols,fatty acids, alkylphenols, sorbitan fatty esters and fattyalkanolamides; thickeners and gel formers, for example fatty alcohols,fatty acids, paraffin oils, fatty esters, methylcellulose, orhydroxyethylcellulose, starch, synthetic polymers such aspolyvinypyrrolidone and polyacrylates, or biopolymers such as alginicacid; stabilizers for peroxo compounds, for example silicates; as wellas complexing agents; perfume oils and hair-care additives such ascationic polymers, lanolin derivatives, cholesterol, pantothenic acid,protein derivatives and protein hydrolyzates, provitamins and vitaminsas well as plant extracts, alkali metal sulfates or alkaline earth metalsulfates, for example sodium sulfate and ammonium sulfate, alkali metalstearates or alkaline earth metal stearates, for example sodiumstearate, and aluminum stearate. In the preparation of the brighteningcolorant of the invention, these additives are used in amounts commonlyemployed for such purposes; for example the surfactants and emulsifiersat a concentration from about 0.2 to 30 weight percent and thethickeners at a concentration from about 0.1 to 30 weight percent(always based on the ready-to-use brightening colorant).

The pH of the ready-to-use brightening colorant is usually from about 6to 12, a pH from about 6.5 to 10.5 and particularly from 7 to 10 beingpreferred.

The pH is preferably adjusted with alkali metal or alkaline earth metalsalts that are alkaline in aqueous solution, for example sodiumcarbonate, sodium hydrogen carbonate, magnesium carbonate, ammoniumcarbonate, ammonium hydrogen carbonate, sodium silicate or mixtures ofthese salts. The concentration of these salts, based on the total amountof the brightening colorant, is from 0.1 to 60 weight percent andparticularly from 0.5 to 55 weight percent.

The brightening colorant of the invention is formulated, in admixturewith the other components usually contained in bleaching agents, as acosmetic composition in the form of a water-free powder or in awater-free, liquid or creamy medium (“coloring paste”). Powderformulations are usually dedusted by spraying with inert carriermaterials, for example paraffin oils, silicone oils, polyethers, fattyesters, polyorganosiloxanes [for example with dimethylpolysiloxanesreferred to in the International Cosmetic Ingredient Dictionary, 5thed., pp. 220/221 (1993) under the name “dimethicone”] or waxes. Suchdedusting methods are known, for example, from U.S. Pat. No. 5,698,186and U.S. Pat. No. 5,891,423.

Depending on the direct dye used, the dyes can also be in the form of anaqueous solution which is stored separately from the water-free peroxysalt-containing composition and which is mixed with the brighteningagent only just before use. The colorant can also be in amicroencapsulated form or packaged in a water-soluble covering (forexample in a polyvinyl alcohol or polyvinylpyrrolidone pouch) andreleased only upon mixing with the peroxide composition.

To use the brightening colorant of the invention, the powder is mixedbefore use with an aqueous hydrogen peroxide preparation to form anapplicable coloring paste, the mixing possibly being carried out in abowl or by shaking in an application bottle. The hydrogen peroxidepreparation used for this purpose (for example an aqueous solution oremulsion) contains about 0.5 to 20 weight percent of hydrogen peroxideor of an addition salt thereof, an amount of 1.5 to 12 weight percentbeing preferred.

The mixing ratio of the colorant of the invention to the hydrogenperoxide preparation is about 1:1 to 1:3 and preferably 1:1.5 to 1:2.

The ready-to-use colorant thus obtained (“coloring paste”) is applieduniformly to dry fibers (particularly human hair). After an exposuretime from about 5 to 80 minutes at 20 to 50° C., preferably 15 to 60minutes at room temperature (20 to 25° C.), or 10 to 50 minutes bysupplying heat (30 to 50° C.), this is followed by rinsing with waterand drying.

The colorant of the invention is preferably packaged together with thehydrogen peroxide preparation in the form of a 2-component kit. It is,however, entirely possible to have the colorant and the hydrogenperoxide preparation in two separate packages.

By means of the colorant of the invention, keratin fibers can bebrightened and colored in a single step, it being possible to colorpreviously dyed hair after a very short time. The colorations achievedwith the colorant of the invention show very high color intensity,covering power and durability.

The following examples will explain the subject matter in greater detailwithout limiting its scope.

EXAMPLES Example 1 Brightening Colorant

Potassium persulfate 20.0 Ammonium persulfate 30.0 Sodium silicate 24.0Magnesium oxide 12.5 Hydroxyethyl cellulose 5.0 Soap beads 6.0 Dispersesilicic acid 2.0 Disodium EDTA 0.5

The dyes were worked into the above-indicated powder base. The resultingcoloring powder was then mixed with 12% aqueous peroxide solution in a1:2 ratio, stirred in a bowl until homogeneous and then applied to dry,dark-blond natural hair. After an exposure time of 20 minutes (Table 1)or 45 minutes (Table 2) at 40° C., the hair was rinsed with warm waterand dried. The dyes used and the coloring result obtained are indicatedin Tables 1 and 2. TABLE 1 Exposure time: 20 minutes at 40° C. ColoringResult (a) 0.5% of dye (b) 2% of dye Dye used CI No. in the brighteningpowder base Acid Yellow 1 10316 (a) yellow (b) lemon yellow FD&C Red 4016035 (a) delicate pink (b) delicate pink Acid Yellow 24 10315 (a)intense brilliant lemon yellow (b) intense brilliant lemon yellow AcidRed 92 45410 (a) intense brilliant pink (b) intense brilliant pinkTetrabromophenol Blue — (a) intense cobalt blue (b) intense cobalt blue3-(2′,6′-Diaminopyridyl- — (a) weak warm yellow 3′-azo)pyridine (b) warmyellow Acid Orange 7 15510 (a) weak orange (b) intense brilliant orangeDisperse Blue 106 — (a) weak gray-green-blue (b) weak gray-green-blueBasic Blue 77 — (a) weak light blue (b) light blue Acid Orange 8 15575(a) red orange (b) red orange Disperse Red 17 11210 (a) dusky pink (b)bluish red Acid Red 51 45430 (a) brilliant pink (b) brilliant pink3′,3″,5′,5″-Tetra- — (a) green blue bromo-m- (b) dark green bluecresolsulfonephthalein 3-Diethylamino-7- 11050 (a) gray brown(4-dimethylamino- (b) gray brown phenylazo)-5-phenyl- phenaziniumchloride 4-(2-Thiazolylazo)- — (a) red orange resorcinol (b) red orangeDithizone — (a) red orange (b) red orange HC Red No. 8 — (a) delicatebluish pink (b) bluish pink 2-Amino-1,4- — (a) orange yellownaphthalenedione (b) orange yellow HC Yellow 13 — (a) intense brilliantlemon yellow (b) intense brilliant lemon yellow Orange IV 13080 (a)orange yellow (b) orange yellow N-(2-Hydroxyethyl)- — (a) intensebrilliant lemon yellow 4-nitroaniline (b) intense brilliant lemon yellow4-Chloro-N-(2,3- — (a) orange yellow dihydroxypropyl)- (b) orange yellow2-nitroaniline

TABLE 2 Exposure time 45 minutes at 40° C. Coloring Result (a) 0.5% ofdye (b) 2% of dye Dye used CI No. in the brightening powder base AcidYellow 1 10316 (a) yellow (b) lemon yellow FD&C Red 40 16035 (a)delicate pink (b) bluish red Acid Yellow 24 10315 a) intense brilliantlemon yellow (b) intense brilliant lemon yellow Acid Red 92 45410 (a)intense brilliant pink (b) intense brilliant pink Tetrabromophenol Blue— (a) intense cobalt blue (b) intense cobalt blue3-(2′,6′-Diaminopyridyl- — (a) warm yellow 3′-azo)pyridine (b) warm darkyellow Acid Orange 7 15510 (a) orange (b) intense brilliant orangeDisperse Blue 106 — (a) weak gray-green-blue (b) weak gray-green-blueBasic Blue 77 — (a) weak light blue (b) light blue Acid Orange 8 15575(a) red orange (b) red orange Disperse Red 17 11210 (a) dusky pink (b)bluish red Acid Red 51 45430 (a) brilliant pink (b) brilliant pink3′,3″,5′,5″-Tetra- — (a) green blue bromo-m- (b) dark green bluecresolsulfonephthalein 3-Diethylamino-7- 11050 (a) light gray(4-dimethylamino- (b) light gray phenylazo)-5-phenyl- phenaziniumchloride 4-(2-Thiazolylazo)- — (a) red orange resorcinol (b) red orangeDithizone — (a) red orange (b) red orange HC Red No. 8 — (a) delicatebluish pink (b) bluish pink 2-Amino-1,4- — (a) orange yellownaphthalenedione (b) orange yellow HC Yellow 13 — (a) intense brilliantlemon yellow (b) intense brilliant lemon yellow Orange IV 13080 (a)orange yellow (b) orange yellow N-(2-Hydroxyethyl)- — (a) intensebrilliant lemon yellow 4-nitroaniline (b) intense brilliant lemon yellow4-Chloro-N-(2,3- — (a) orange yellow dihydroxypropyl)- (b) orange yellow2-nitroaniline

Example 2 Brightening Colorant

Potassium persulfate 20.0 Ammonium persulfate 30.0 Sodium silicate 24.0Magnesium oxide 12.5 Hydroxyethylcellulose 5.0 Soap beads 6.0 Dispersesilicic acid 2.0 Disodium EDTA 0.5

The dyes indicated in Table 3 together with 0.5% of Acid Red 92 wereworked into the above-described brightening powder base. The resultingcoloring powder was then mixed with a 12% aqueous peroxide solution in a1:2 ratio and stirred in a mixing bowl until homogeneous, after which itwas applied to dry dark-brown natural hair. After an exposure time of 20minutes at 40° C., the strands were rinsed with warm water and dried.TABLE 3 Dye used (Amount in %) CI No. Coloring Result Acid Yellow 1(0.5) 10316 intense brilliant pink Acid Yellow 24 (0.5) 10315 red AcidYellow 24 (2.0) 10315 red Tetrabromophenol (0.5) — violet BlueTetrabromophenol (2.0) — intense warm blue Blue Acid Orange 7 (0.5)15510 intense brilliant pink Acid Orange 7 (2.0) 15510 brilliant redDisperse Blue 106 (0.5) — bluish red Disperse Blue 106 (2.0) — bluishred Basic Blue 77 (0.5) — bluish red Basic Blue 77 (2.0) — bluish redAcid Orange 8 (0.5) 15575 intense brilliant pink Acid Orange 8 (2.0)15575 intense brilliant pink Disperse Red 17 (0.5) 11210 intensebrilliant pink Disperse Red 17 (2.0) 11210 intense pink

Example 3 Brightening Colorant

Potassium persulfate 20.0 Ammonium persulfate 30.0 Sodium silicate 24.0Magnesium oxide 12.5 Hydroxyethylcellulose 5.0 Soap beads 6.0 Dispersesilicic acid 2.0 Disodium EDTA 0.5 Acid Red 92 (CI 45410) 0.01Tetrabromophenol Blue 0.01 Basic Blue 77 0.10

The above coloring powder was mixed with a 12% aqueous peroxide solutionin a 1:2 ratio in a mixing bowl until homogeneous and then applied todry, oxidatively dyed light-brown hair. After an exposure time of 20minutes at 40° C., the strands were rinsed with warm water and dried.

The hair was colored to a delicate bluish pink shade.

Example 4 Brightening Colorant

Potassium persulfate 20.0 Ammonium persulfate 30.0 Sodium silicate 24.0Magnesium oxide 12.5 Hydroxyethylcellulose 5.0 Soap beads 6.0 Dispersesilicic acid 2.0 Disodium EDTA 0.5 Acid Red 92 (CI 45410) 0.1 AcidYellow 1 (CI 10316) 0.2 Acid Yellow 24 (CI 10315) 0.8 Acid Orange No. 8(CI 15575) 1.0 Acid Orange No. 7 (CI 15510) 1.0

The above coloring powder was mixed with a 12% aqueous peroxide solutionin a 1:2 ratio in a mixing bowl until homogeneous and then applied todry, oxidatively dyed black hair. After an exposure time of 20 minutesat 40° C., the strands were rinsed with warm water and dried.

The hair was colored to a brilliant orange shade.

Example 6 [sic] Brightening Colorant

Brightening Coloring Powder Potassium persulfate 20.00 Ammoniumpersulfate 30.00 Sodium silicate 24.00 Magnesium oxide 12.50Hydroxyethylcellulose 5.00 Soap beads 6.00 Disperse silicic acid 2.00Disodium EDTA 0.50 Acid Red 92 (CI 45410) 0.10 Acid Yellow 1 (CI 10316)0.15 Acid Yellow 24 (CI 10315) 0.05 Acid Orange No. 8 (CI 15575) 0.02Acid Orange No. 7 (CI 15510) 0.20 3-(2′,6′-Diaminopyridyl-3′-azo)- 0.10pyridine Acid Red 51 (CI 45430) 0.20 3′,3″,5′,5″-Tetrabromo-m-cresol-0.20 sulfonephthalein Tetrabromophenol Blue 0.05 Disperse Blue 106 0.10Basic Blue 77 0.10 Disperse Red 17 (CI 11210) 0.01

The above coloring powder was mixed with a 12% aqueous peroxide solutionin a 1:2 ratio in a mixing bowl until homogeneous and then applied todry, oxidatively dyed black hair. After an exposure time of 20 minutesat 40° C., the strands were rinsed with warm water and dried.

The hair was colored to a gray brown shade.

Unless otherwise indicated, all percentages given in the present patentapplication are by weight.

1. Agent for the simultaneous brightening and coloring of keratinfibers, characterized in that it contains at least one peroxy salt andat least one dye resistant to peroxy salts which is taken from the groupconsisting of azo dyes, quinone dyes, triphenylmethane dyes, acid dyesand basic dyes [sic].
 2. Agent according to claim 1, characterized inthat the dye resistant to peroxy salts is selected from among3(2′,6′-diaminopyridyl-3′-azo)pyridine;2-[(4-ethyl-(2-hydroxyethyl)-amino]-2-methylphenyl)azo]}-nitro-1,3-thiazole;N N-di(2-hydroxyethyl)-3-methyl-4-[(4-nitrophenyl)azo]aniline;3-diethylamino-7-(4-dimethylaminophenylazo)-5-phenylphenaziniumchloride; 4-(2-thiazolylazo)resorcinol; sodium4-[(4-phenylamino)azo]benzenesulfonate;1-[(3aminopropyl)amino-9,10-anthracenedione;3′,3″,4,5,5′,5″,6,7-abromophenolsulfone-phthalein;1-[(4-amino-3,5-dimethylphenyl)-(2,6-dichlorophenyl)methylene]-3,5-dimethyl-4-imino-2,5-cyclohexadienephosphoric acid (1:1) (Basic Blue 77);3′,3″,5′,5″-tetrabromo-m-cresolsulfonephthalein; disodium2,4-dinitro-1-naphthol-7-sulfonate; sodium4-2′-hydroxy-1′-naphthyl)-azo]benzenesufonate;3′,6′-dihydroxy-2′,4′,5′,7′-tetraiodospiro-[(isobenzofuran-1(3H)-9′(9H)-xanthen]-3-onedisodium salt; disodium6-hydroxy-5-[(2-methoxy-5-methyl-4-sulfophenyl)azo]-2-naphthalenesulfonate;2,4-dinitro-1-naphthol sodium salt;2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachloro-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),9′(9H)xanthene]-3-one disodium salt; sodium4-(2-hydroxy-1-naphthylazo)-3-methylbenzenesulfonate;2-amino-1,4-naphtalenedione; dithizone;N-(2-hydroxyethyl)-2-nitro-4-(trifluoromethyl)aniline;N-(2-hydroxyethyl)-4-nitroaniline and4-chloro-N-(2,3-dihydroxypropyl)-2-nitroaniline.
 3. Agent according toclaim 1, characterized in that it contains the dye in an amount from0.001 to 10 weight percent.
 4. Agent according to claim 1, characterizedin that the peroxy salt is selected from among sodium persulfate,potassium persulfate, ammonium persulfate or mixtures of saidpersulfates.
 5. Agent according to claim 1, characterized in that itcontains the peroxy salt in a total amount from 0.1 to 50 weightpercent.
 6. Agent according to claim 1, characterized in that in theready-to-use condition it has a pH of 6 to
 12. 7. Two-component kitconsisting of a colorant and a hydrogen peroxide preparation,characterized in that the colorant is an agent according to claim
 1. 8.Agent according to claim 7, characterized in that the hydrogen peroxidepreparation is an aqueous solution or emulsion.
 9. Agent according toclaim 7, characterized in that the hydrogen peroxide preparationcontains from 0.5 to 20 weight percent of hydrogen peroxide or anaddition salt thereof.